Aqueous polyurethane - vinyl polymer hybrid dispersions

ABSTRACT

The invention relates to aqueous polyurethane-vinyl polymer hybrid dispersions comprising, as building blocks hydrophobically modified hydroxy-functional polyesters A, acids B that have further groups which react with isocyanates under formation of urethanes, ureas, or thiourethanes, compounds G having only one hydroxyl group, and one or more tertiary amino groups, olefinically unsaturated monomers H2 having a polymerisable ethylenic unsaturation and a further functional group which reacts with an isocyanate group under bond formation, olefinically unsaturated monomers H1 having at least one polymerisable ethylenic unsaturation and no further functional group which reacts with an isocyanate group, and multifunctional isocyanates I having at least two isocyanate groups per molecule, to a process of their preparation, and to a method of use thereof.

FIELD OF THE INVENTION

The present invention relates to aqueous polyurethane-vinyl polymerhybrid dispersions which are prepared by polymerisation, initiated byfree radicals, of ethylenically unsaturated monomers and polyurethaneprepolymers containing acid groups and hydroxyl groups, to a method fortheir preparation, and to their use particularly as coating binder inmultilayer coatings.

BACKGROUND OF THE INVENTION

Dispersions of polyurethane-vinyl polymer hybrids made by radicallyinitiated copolymerisation of ethylenically unsaturated monomers andpolyurethane macromonomers have been known, i.a. from EP 0 522 420 A2.These dispersions have been used in a variety of applications, includingpreparation of basecoats in multilayer coatings used for the painting ofcars. In such multilayer applications, a key property of the coatinglayers is their intercoat adhesion, in this case, between theprimer-surfacer layer, and the basecoat, and the basecoat layer and theclearcoat which is the topmost coating layer. Another property that isimportant for the basecoat is its water and humidity resistance, whichneeds constant improvement.

SUMMARY OF THE INVENTION

It has been found in the experiments underlying this invention that anaqueous polyurethane-vinyl polymer hybrid dispersion made bypolymerisation, initiated by free radicals, of a mixture ofethylenically unsaturated monomers having hydroxyl groups, in thepresence of multifunctional isocyanates and polyurethane prepolymerscontaining acid groups and hydroxyl groups which prepolymers are basedon polyurethanes made from hydrophobically modified polyesters lead toimproved basecoat coating compositions.

The invention therefore relates to aqueous polyurethane-vinyl polymerhybrid dispersions comprising a polyurethane-vinyl polymer hybrid UV,and water, wherein the polyurethane-vinyl polymer hybrid UV isdispersed. The building blocks of the aqueously dispersedpolyurethane-vinyl polymer hybrid comprise

-   -   hydrophobically modified hydroxy-functional polyesters A,    -   acids B that have further groups which react with isocyanates        under formation of urethanes, ureas, or thiourethanes,    -   optionally, hydroxy-functional oligomeric or polymeric compounds        C which may be polyesters, polycarbonates, polyethers,        polyamides, polydienes and polyenes, and which have at least two        hydroxyl groups per molecule,    -   optionally, monomeric hydroxy compounds D having at least two        hydroxyl groups per molecule,    -   optionally, compounds E having at least one primary or secondary        amino group, and at least one hydroxyl group per molecule,    -   optionally, compounds F having two or more primary or secondary        amino groups per molecule and no hydroxyl groups,    -   compounds G having only one hydroxyl group, and one or more        tertiary amino groups,    -   olefinically unsaturated monomers H comprising monomers H2        having a polymerisable ethylenic unsaturation and a further        functional group which reacts with an isocyanate group under        bond formation, and olefinically unsaturated monomers H1 having        at least one polymerisable ethylenic unsaturation and no further        functional group which reacts with an isocyanate group, and    -   multifunctional isocyanates I having at least two isocyanate        groups per molecule.

The hydrophobically modified polyesters A have side chains with chainlength of preferably from four to twenty carbon atoms, and arepreferably obtained by reaction of a polyester A′ having residualhydroxyl and acid groups, by reaction of the acid groups with amonofunctional compound A4 having an epoxide or aziridine functionality,and a linear or branched alkyl residue of at least four carbon atoms, inwhich reaction at least 90% of the remaining acid groups are convertedto ester or amide groups which groups link the side chains to thepolyester main chain.

It has been found that polyurethane-vinyl polymer hybrid dispersionshaving such hydrophobically modified polyesters A as building blocksyield coating films with improved interlayer adhesion, and increasedwater and humidity resistance.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hydrophobically modified polyesters A are preferably made frompolyesters A′ based on aliphatic diols A1 and aliphatic and/or aromaticdiacids A2, or on monohydroxymonoacids A3, having one hydroxyl group andone acid group per molecule, or mixtures of these starting materials.Small amounts, such as up to 10% of the amount of substance of dihydroxycompounds, or up to 10% of the amount of substance of diacids, or up to10% of the amount of substance of the monohydroxymonoacids, may bereplaced by higher functional compounds of the same kind, i.e. by triolsA11, triacids A21, or hydroxy acids A31 having more than one functionalhydroxyl or acid group. In the first step of the synthesis of thepolyesters A, the mixture of hydroxy-functional and acid-functionalcompounds A1, A2, A3, and optionally, A11, A21, and A31 is esterified atelevated temperature of up to 250° C., under removal of the water formedin the polycondensation reaction, and optionally, in the presence of anesterification catalyst. The stoichiometry is preferably chosen suchthat the hydroxyl value of the resulting polyester A′ is at least 20mg/g, and up to 100 mg/g. A low acid number of preferably not more than5 mg/g is obtained. The polyester A′ formed in this reaction is thentreated at a temperature of preferably from 150° C. to 220° C. with acompound A4 which may be a monoepoxide compound or a monoaziridinecompound which reacts with the acid groups of the polyester A′ underaddition and formation of an ester or an amide group, and of a hydroxylor amino group by ring opening of the oxirane or aziridine ring. Thepolyesters A which are formed by reaction of the polyesters A′ with thecompound A4 preferably have a remaining acid number of 0.1 mg/g or less.Their hydroxyl number is preferably at least 22 mg/g, and alsopreferably, not more than 105 mg/g.

The acid value or acid number w_(Ac) is defined, according to DIN EN ISO2114 (DIN 53 402), as the ratio of that mass m_(KOH) of potassiumhydroxide which is needed to neutralise the sample under examination,and the mass m_(B) of this sample, or the mass of the solids in thesample in the case of a solution or dispersion; its customary unit is“mg/g”. This value is determined in the examples according to thisstandard.

The hydroxyl value or hydroxyl number w_(OH) is defined according to DINEN ISO 4629 (DIN 53 240) as the ratio of the mass of potassium hydroxidem_(KOH) having the same number of hydroxyl groups as the sample, and themass m_(B) of that sample (mass of solids in the sample for solutions ordispersions); the customary unit is “mg/g”. This value is determined inthe examples according to this standard. Preferred compounds A1 arelinear, branched, and cyclic aliphatic dihydroxy compounds preferablyhaving from two to twelve carbon atoms. Preferred are 1,2-ethanediol,1,2- and 1,3-propanediol, 1,2- and 1,4-butanediol,2,2-dimethyl-1,3-propanediol (neopentylglycol),2-methyl-2,4-pentanediol, 1,4-bis-hydroxymethylcyclohexane, and theso-called bifunctional fatty alcohols which are alpha-,omega-dihydroxyalkanes with from six to twenty-five carbon atoms,particularly 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol,1,12-dodecanediol, 1,13-tridecanediol, 1,18-octadecanediol,1,21-heneicosanediol, and 1,25-pentacosanediol, and alsocarbohydate-based etheralcohols such as the 1,4:3,6-dianhydrohexitolsisosorbide, isomannide, and isoidide. The longer-chain alcohols amongthese can also contribute to increased hydrophobicity, and highertoughness of the coating layers made from polyurethane-vinyl polymerhybrids prepared therewith.

Preferred compounds A2 are aliphatic dicarboxylic acids having fromthree to twelve carbon atoms, such as malonic acid, succinic acid,glutaric acid, adipic acid, octanedioic acid, and also dimeric fattyacids having up to forty carbon atoms, and also aromatic dicarboxylicacids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acids.

Preferred compounds A3 are hydroxybenzoic acid, lactic acid,gamma-hydroxybutyric acid, delta-hydroxyvaleric acid, andepsilon-hydroxycaproic acid.

Preferred compounds A11 are glycerol, trimethylolethane,trimethylolpropane, pentaerythritol, ditrimethylolethane,ditrimethylolpropane, dipentaerythritol, erythritol, threitol, andmannitol.

Preferred compounds A21 are trimellithic acid, trimesic acid,carballylic acid, and aconitic acid.

Preferred compounds A31 are citric acid, tartaric acid, alpha-, beta-and gamma-resorcylic acid, (3,5-dihydroxybenzoic acid,2,4-dihydroxybenzoic acid, and 2,6-dihydroxybenzoic acid), and gentisicacid (2,5-dihydroxybenzoic acid).

Preferred compounds A4 are glycidol (2,3-epoxy-1-propanol), and ethersand esters thereof such as glycidyl acetate, glycidyl propionate,glycidyl butyrate, glycidyl pivalate, glycidyl 2-ethylhexanoate,glycidyl 2,2-dimethyloctanoate, commercial mixtures of the ester ofglycidol with a mixture of isomeric alpha-branched decanoic acids,lauryl glycidyl ether, and stearyl glycidyl ether. Other usefulmonoepoxides are epoxidised alkenes, such as 1,2-epoxhexane,1,2-epoxydecane, 1,2-epoxydodecane, and 1,2-epoxyoctadecane, andalkylaziridines preferably having from six to twelve carbon atoms suchas hexylaziridine, heptylaziridine, nonylaziridine, anddodecylaziridine.

The acids B that have further groups which react with isocyanates underformation of urethanes, ureas, or thiourethanes preferably have at leastone hydroxyl, amino or thiol group, and an acid group which ispreferably a carboxylic acid group or a sulfonic acid group, and aremore preferably selected from the group consisting of2,2-(bis-hydroxymethyl)acetic acid, 2,2-(bishydroxymethyl)-propionicacid, 2,2-(bishydroxymethyl)butyric acid, and 2-aminoethanesulfonicacid.

The hydroxy-functional oligomeric or polymeric compounds C which areoptionally used may be polyesters, poly-carbonates, polyethers,polyamides, polydienes and polyenes, and which have at least twohydroxyl groups per molecule include polyhydroxy-polyethers of theformula

H—[—O—(CHR)_(n)—]_(m)OH

in which R is hydrogen or a lower alkyl radical, optionally with varioussubstituents, n is a number from 2 to 6 and m is a number from 10 to120.

Examples are poly(oxytetramethylene) glycols, poly(oxyethylene) glycolsand poly(oxy-propylene) glycols. The preferred polyhydroxy-polyethersare poly(oxypropylene) glycols having a molar mass in the range from 400g/mol to 5000 g/mol.

The polyhydroxy-polyesters are prepared by esterification of organicpolycarboxylic acids or their anhydrides with organic polyols. Thepolycarboxylic acids and the polyols can be aliphatic or aromaticpolycarboxylic acids and polyols.

The polyols used for the preparation include those mentioned under A1,and also, in a mass fraction of not more than 10%, based on the mass ofthe polyols used in the polyhydroxy-polyesters, trishydroxyalkylalkanes,such as, for example, trimethylolpropane, andtetrakishydroxyalkylalkanes, such as, for example, pentaerythritol.

The acid component of the polyesters primarily consists of low molarmass polycarboxylic acids or their anhydrides having from two toeighteen carbon atoms in the molecule. Suitable acids are, for example,phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalicacid, hexahydrophthalic acid, succinic acid, adipic acid, azelaic acid,sebacic acid, maleic acid, glutaric acid, hexachloroheptanedicarboxylicacid, alkyl- and alkenylsuccinic acid, for example n-octenylsuccinicacid and n- and iso-dodecenylsuccinic acid, tetrachlorophthalic acid,trimellithic acid and pyromellithic acid. Instead of these acids, theiranhydrides, where these exist, can also be used. Dimeric and trimericfatty acids can also be employed as the polycarboxylic acids.

The terms polyhydroxy-polyether and polyhydroxy-polyester are also to beunderstood as meaning those products of this type which contain monomershaving carboxyl, phosphonic acid or sulfonic acid groups.

Polyhydroxy-polyesters which are derived from lactones can furthermorebe used in the invention.

These products are obtained, for example, by reaction of a lactone witha polyol. Such products are described in U.S. Pat. No. 3,169,945.

The polylactone-polyols which are obtained by this reaction aredistinguished by the presence of a terminal hydroxyl group and byrecurring polyester contents which are derived from the lactone.

The lactone used as the starting material can be any desired lactone orany desired combination of lactones, and this lactone should contain atleast four carbon atoms in the ring, for example from five to eightcarbon atoms, and two hydrogen atoms should be directly bonded to thecarbon atom bonded to the oxygen group of the ring.

Preferred lactones are the caprolactones. The most preferred lactone isunsubstituted epsilon-caprolactone. This lactone is particularlypreferred, since it is available in large amounts and produces coatingswhich have excellent properties. Various other lactones can furthermorebe used individually or in combination.

Examples of aliphatic polyols which are suitable for the reaction withthe lactone are ethylene glycol, 1,3-propanediol, 1,4-butanediol,1,6-hexanediol, dimethylolcyclohexane, trimethylol-propane andpentaerythritol.

Possible starting compounds are furthermore polycarbonate-polyols andpolycarbonate-diols These OH-functional polycarbonates can be preparedby reaction of polyols, such as 1,3-propanediol, 1,4-butanediol,1,6-hexanediol, diethylene glycol, triethylene glycol,1,4-bishydroxymethylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane,neopentylglycol, trimethylolpropane or pentaerythritol, withdi-carbonates, such as dimethyl, diethyl or diphenyl carbonate, orphosgene. Mixtures of such polyols can likewise be employed. Mixtures ofpolyhydroxy-polyethers, polyhydroxy-polyesters andpolyhydroxy-polycarbonates are likewise possible.

Further oligomeric or polymeric hydroxy-functional compounds arepolyamides, polydienes and polyenes where the oligomer or polymer chainis a polyamide, a polyene or a polydiene, and there are at least two,preferably terminal, hydroxyl groups per molecule. Particularlypreferred are dihydroxy compounds based on polybutadiene, or onhydrogenated polybutadiene. These compounds also contribute tohydrophobicity and toughness of the coating layer made from apolyurethane-vinyl polymer hybrid comprising these building blocks.

The monomeric hydroxy compounds D having at least two hydroxyl groupsper molecule, which are optionally used, are aliphatic diols which maybe linear, branched or cyclic, and have from two to forty carbon atoms.Preferred compounds D are 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,2-and 1,4-butanediol, 2,2-dimethyl-1,3-propanediol (neopentylglycol),2-methyl-2,4-pentanediol, 1,4-bis-hydroxymethylcyclohexane, and theso-called bifunctional fatty alcohols which are alpha-,omega-dihydroxyalkanes with from six to twenty-five carbon atoms,particularly 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol,1,12-dodecanediol, 1,13-tridecanediol, 1,18-octadecanediol,1,21-heneicosanediol, and 1,25-pentacosanediol, and alsocarbohydate-based etheralcohols such as isosorbide, isomannide, andisoidide. The longer-chain alcohols among these can also contribute toincreased hydrophobicity, and higher toughness of the coating layersmade from polyurethane-vinyl polymer hybrids prepared therewith.

It is possible to use one or both of compounds C and D.

The compounds E which are optionally used, have one primary or secondaryamino group, and at least one hydroxyl group per molecule, such as2-aminoethanol, and may have preferably secondary amino groups, and twohydroxyl groups. Preferred compounds are selected from the groupconsisting of the monohydroxymonoamines 2-aminoethanol,2-methylaminoethanol, and 3-aminopropanol, the dihydroxymonoamines2-amino-1,3-propanediol, diethanolamine, and 1,1′-iminodi-2-propanol(diisopropanolamine). These compounds are optionally used, and reactwith an isocyanate group preferably to form a urea, and they canintroduce additional hydroxyl groups into the polymer formed.

The compounds F having two or more amino groups per molecule, and nohydroxyl groups, are aliphatic linear or branched diamines having fromtwo to ten carbon atoms and at least two primary amino groups, such as1,4-diaminobutane, 1,6-diaminohexane, and 2-methyl-1,5-diaminopentane.These compounds are optionally used, and provide chain extension underformation of urea groups by reacting with isocyanate-functionalcompounds formed during the synthesis.

It is preferred to use at least one of compounds E and F.

The compounds G having not more than one hydroxyl group, and at leastone tertiary amino group, are preferably aliphatic, linear, branched orcyclic, and have from four to twelve carbon atoms; preferred compoundsare N—N-dimethylaminoethanol, 1-dimethylamino-2-propanol,1-dimethylamino-3-propanol, and also N-(2-hydroxyethyl)piperazine. Thesecompounds are used as neutralising agents.

The olefinically unsaturated compounds H comprise monomers H2 which arehydroxy-functional monomers H2 having an olefinic unsaturation which areradically polymerisable, and also, olefinically unsaturated monomers H1that are radically copolymerisable and do not have functional groups intheir molecules that can react with an isocyanate group. The monomers H2preferably have at least one hydroxyl group, more preferably one or twohydroxyl groups, and most preferably two hydroxyl groups, and arepreferably partial esters of polyhydric alcohols having at least twohydroxyl groups, and olefinically unsaturated carboxylic acids selectedfrom the group consisting of acrylic acid, methacrylic acid, and theirhomologues such as vinylacetic acid, crotonic acid and isocrotonic acid.Preferred monomers H2 are hydroxyethyl(meth)acrylate,hydroxypropyl-(meth)acrylate, glycerol mono(meth)acrylate,trimethylolpropane mono(meth)acrylate, where “(meth)acrylate” stands for“acrylate or methacrylate”. Preferred monomers H1 are esters of(meth)acrylic acid with aliphatic linear, branched or cyclicmonoalcohols having from one to twelve carbon atoms in the alkyl group,particularly methyl (meth)acrylate, ethyl (meth)acrylate, butyl(meth)-acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, andisobornyl (meth)acrylate, and also, copolymerisable vinyl monomers suchas styrene, vinyltoluene, acrylonitrile, and methacrylonitrile. It isalso possible to replace up to 10% of the mass of the mono-unsaturatedmonomers by mono-mers having two or more olefinically unsaturatedgroups, such as hexandioldi(meth)-acrylate or trimethylolpropanetri(meth)acrylate.

The multifunctional isocyanates I having at least two isocyanate groupsper molecule are aromatic or aliphatic or mixed aliphatic-aromaticisocyanates, and preferably selected from the group consisting oftrimethylene diisocyanate, tetramethylene diisocyanate, pentamethylenediisocyanate, hexamethylene diisocyanate (HDI), propylene diisocyanate,ethylethylene diiso-cyanate, 2,3-dimethylethylenediisocyanate,1-methyltrimethylene diisocyanate, cyclopentylene 1,3-diisocyanate,cyclohexylene 1,4-diisocyanate, cyclohexylene 1,2-diisocyanate,phenylene 1,3-diisocyanate, phenylene 1,4-diisocyanate, toluylene2,4-diisocyanate, toluylene 2,6-diiso-cyanate, biphenylene4,4′-diisocyanate, bis-(4-isocyanatophenyl)methane (MDI), naphthylene1,5-diisocyanate, naphthylene 1,4-diisocyanate,1-isocyanatomethyl-5-isocyanato-1,3,3-tri-methylcyclohexane (IPDI),bis-(4-isocyanatocyclohexyl)methane (H12-MDI),4,4′-diiso-cyanato-diphenyl ether,2,3-bis-(8-isocyanatooctyl)-4-octyl-5-hexylcyclohexene,trimethylhexa-methy-lene diisocyanates, tetramethylxylylenediisocyanates, uretdiones of the above diisocyanates, isocyanurates ofthe above diisocyanates and allophanates of the above diisocyanates.Mixtures of such di- or polyisocyanates can likewise be employed.

Mixtures of two or more of the mentioned compounds can also be used, forall the compounds listed supra.

The amounts of these educts, or starting materials for thepolyurethane-vinyl polymer hybrid UV are chosen such that the followingconditions are preferably met:

-   -   a) the mass fraction w(A)=m(A)/m(UV) of hydrophobically modified        polyester A in the polyurethane-vinyl polymer hybrid UV, where        m(A) is the mass of the polyester A, and m(UV) is the mass of        the polyurethane-vinyl polymer hybrid UV, is from 20% to 60%        (from 20 g/[100 g] to 60 g/[100 g]), particularly preferably        from 25% to 55%,    -   b) the ratio of the amount of substance of hydrophobic modifier        A4 in the polyester A to the amount of substance of residual        acid groups in the polyester A′ is from 1.1 mol/mol to 1.7        mol/mol, particularly preferably from 1.2 mol/mol to 1.6        mol/mol, and especially preferred, from 1.25 mol/mol to 1.5        mol/mol,    -   c) the mass fraction w(H)=m(H)/m(UV) of olefinically unsaturated        monomers H in the polyurethane-vinyl hybrid polymer UV is from        10% to 60%, particularly preferably from 25% to 50%,    -   d) the glass transition temperature T_(g) of the vinyl polymer        part is lower than, or equal to, 20° C., and particularly        preferably, lower than, or equal to, 0° C., if the mass fraction        w(H) as defined supra is 35% or more, which condition is        particularly favourable to achieve a low degree of blistering,    -   e) the mass fraction w(H2)=m(H2)/[m(H1)+m(H2)] of        hydroxy-functional monomers H2 in the olefinically unsaturated        monomers H is from 5% to 35%, particularly preferably from 7% to        30%.

In a particularly preferred embodiment, at least two of these conditionsare fulfilled, viz., a) and b); a) and c); a) and d); a) and e); b) andc); b) and d); b) and e); c) and d); c) and e); and d) and e). Morepreferably, at last three of these conditions are fulfilled, viz. a), b)and c); a), b) and d); a), b) and e); a), c), and d); a), c), and e);a), d), and e); b), c), and d); b), c), and e); b), d), and e), and c),d), and e). Still more preferably, four of these conditions arefulfilled, viz., a), b), c), and d); a), b), c) and e); and b), c), d)and e). Most preferred, all conditions a), b), c), d), and e) arefulfilled.

When stating mass fractions of educts in the addition polymer UV, thehydroxy-functional educts are always referred to in their hydroxyl form,having —OH end groups, and the amino-functional educts are alwaysreferred to in their amine form having >NH or —NH₂ end groups, etc.Likewise, isocyanates are referred to in their isocyanate-functionalform having —N═C═O end groups, and olefinically unsaturated monomers arereferred to in their olefinically unsaturated form.

The polyesters A′ are made in a polyesterification process wherein amixture of aliphatic diols A1 and aliphatic and/or aromatic diacids A2,optionally in the presence of hydroxyacids A3, and further optionally,in the presence of one or more of hydroxy compounds A11 having more thantwo hydroxyl groups, acid compounds A21 having more than two acidgroups, preferably carboxyl groups, and hydroxyacids A31 having morethat one hydroxyl group or more than one acid group, or at least twohydroxyl groups and at least two acid groups, is esterified at elevatedtemperature of up to 250° C., under removal of the water formed in thepolycondensation reaction.

In a second step, the polyester A′ formed in the first step havingresidual hydroxyl and acid groups is treated at a temperature ofpreferably from 150° C. to 220° C. with a monofunctional compound A4selected from the group consisting of a monoepoxide compound and amonoaziridine compound whereby preferably at least 90% of the acidgroups of the polyester A′ are consumed under addition and formation ofan ester or an amide group, and of a hydroxyl or amino group by ringopening of the oxirane or aziridine ring. Hydrophobically modifiedpolyesters A are obtained having an acid number of 0.1 mg/g or less.

The hydrophobically modified polyesters A are then mixed with acids Bthat have further groups which react with isocyanates under formation ofurethanes, ureas, or thiourethanes, optionally, hydroxy-functionaloligomeric or polymeric compounds C which may be polyesters,poly-carbonates, polyethers, polyamides, polydienes and polyenes, andwhich have at least two hydroxyl groups per molecule, and furtheroptionally, monomeric hydroxy compounds D having at least two hydroxylgroups per molecule. The use of compounds C is optional, as well as theuse of compounds D, where it is possible to use only C, only D, both Cand D, or none of both.

The mixture of A, B, C (if used), and D (is used) is then heated understirring preferably to at least 60° C., to form a homogeneous solution,and then reacted by addition of a substoichiometric quantity of themultifunctional isocyanate I preferably over a time of from twentyminutes to one hundred and twenty minutes, depending on the size of thelot, and keeping the reaction temperature in a range of from 60° C. to150° C. An intermediate also referred to as “prepolymer” is formed whichhas hydroxyl functional groups. By “substoichiometric”, it is meant thatthe amount of substance of isocyanate groups in the quantity ofmultifunctional isocyanate I added is less than the sum of the amountsof substance of isocyanate-reactive groups, in this case, hydroxylgroups, of the compounds A, B, C, and D present in this reaction. At theend of this stage of the reaction, no more unreacted isocyanate groupsare present in the reaction mixture.

To this prepolymer, a solution is then added which comprises at leastone olefinically unsaturated monomer H1 having no further functionalgroup other than one or more vinyl or polymerisable olefinicallyunsaturated groups, and at least one olefinically unsaturated monomer H2having at least one hydroxyl group and a vinyl or polymerisableolefinically unsaturated group, optionally, an antioxidant or radicalscavenger is also added which is preferably a sterically hinderedphenol, such as a phenol having bulky substituents, preferablytert-butyl groups, in the 2- and 6-positions, and an alkyl substituentin the 4-position, further optionally, a solvent S which is inert in thereaction, and the solution and the prepolymer are homogenised. To thishomogeneous mixture, further multifunctional isocyanate I is added, thistime in stoichiometric excess so that the amount of substance ofisocyanate groups n(NCO) exceeds the sum n(OH, Σ) of the amounts ofsubstance of isocyanate-reactive groups, in this case, hydroxyl groups,by at least 2%, in other words, n(NCO)/n(OH, Σ)≥1.02 mol/mol. A mixtureis then added which comprises the compounds E (if used), F (if used),and G, as well as water, and the resulting mixture is homogenised wellfor preferably from thirty to ninety minutes before adding an aqueoussolution of a radical initiator, preferably an alkyl hydroperoxide,homogenised again, and then, preferably, an aqueous solution of areducing agent, preferably ascorbic acid, is added. The polymerisationreaction is continued for preferably from one hour to four hours, afterwhich time, the resulting dispersion of the polyurethane-vinyl polymerhybrid UV is cooled to room temperature and filtered.

It is possible to vary the degree of polymerisation of the resultingpolyurethane-vinyl polymer hybrid, by adjusting the stoichiometry of thepolyurethane part and also by selecting the amount of radical initiatorand reducing agent, and also by varying the ratio of the mass m(U) ofthe polyurethane part (stemming from compounds A, B, C, D, E, F, and I),to mass m(H) of the vinyl polymer stemming from compounds H.

The dispersions of the polyurethane-vinyl polymer hybrid UV according tothe invention are suitable for diverse uses, for example for thepreparation of coating systems, inter alia for coating wood, as bindersfor water-dilutable adhesives or as resins for printing inks.

They can be combined with and are in general compatible with otheraqueous dispersions and solutions of plastics, for example acrylicand/or methacrylic polymers, polyurethane, polyurea resins, polyesterresins and epoxy resins, thermoplastics based on polyvinyl acetate,-vinyl chloride, -vinyl ether, -chloroprene and -acrylonitrile andethylene/butadienestyrene copolymers. They can also be combined withsubstances which have a thickening action and are based on polyacrylatesor polyurethanes containing carboxyl groups, hydroxyethyl-cellulose,polyvinyl alcohols and inorganic thixotropic agents, such as bentonite,sodium-magnesium silicates and sodium-magnesium-fluorine-lithiumsilicates.

The polyurethane-vinyl polymer hybrid dispersions according to theinvention can be applied to the most diverse substrates, for exampleceramic, wood, glass, concrete and preferably plastics, such aspolycarbonate, polystyrene, polyvinyl chloride, polyester,poly(meth)acrylates, acrylonitrile/butadiene/styrene polymers and thelike, and preferably to metal, such as iron, copper, aluminum, steel,brass, bronze, tin, zinc, titanium, magnesium and the like. They adhereto the various substrates without adhesion-promoting primers orintermediate layers.

The polyurethane-vinyl polymer hybrid dispersions according to theinvention are suitable, for example, for the production ofcorrosion-preventing coatings and/or intermediate coatings for the mostdiverse fields of use, in particular for the production of metallic andsolid base paints in multi-coat build-ups of paint for the fields ofpainting of automobiles and plastics, and for producing primer paintsfor the field of painting of plastics.

Because of the short flush-off times of the base paints based on thepolyurethane-vinyl polymer hybrid dispersions according to theinvention, the pigmented coat of base paint can be over-varnished with aclear varnish without a stoving step (wet-in-wet process) and thecoatings can then be stoved together or subjected to forced drying. Basepaints prepared with the polyurethane-vinyl polymer hybrid dispersionsaccording to the invention give paint films of the same quality largelyindependently of the stoving or drying temperature, so that they can beemployed both as a repair paint for motor vehicles and as a stovingpaint for series painting of motor vehicles. In both cases, paint filmsresult having a good adhesion to the original coating and a goodresistance to condensation water.

The crosslinking agents customary in the paint industry, such as, forexample, water-soluble or -emulsifiable aminoplast crosslinkers such asurea, cyclic urea, melamine or benzoguanamine resins, polyisocyanates orprepolymers having terminal isocyanate groups, water-soluble orwater-dispersible polyaziridines and blocked polyisocyanates, can beadded during formulation of water-dilutable paints using thepolyurethane-vinyl polymer hybrid dispersions according to theinvention. The aqueous coating systems can contain all the inorganic ororganic pigments and dyestuffs which are known and are customary inpaint technology, as well as wetting agents, foam suppressants, flowcontrol agents, stabilisers, catalysts, fillers, plasticisers andsolvents. The coating composition is completed to a paint by adding theusual additives, such as thickeners, flow modifiers, wetting agents,light stabilisers, and pigments, particularly metal flake pigments. Thepaint obtained is the applied to a substrate, and hardened bycrosslinking the paint to form a coating film on the substrate, byheating the coated substrate to a temperature of preferably from 50° C.to 180° C.

The polyurethane-vinyl polymer hybrid dispersions according to theinvention can also be used directly for gluing any desired substrates.To achieve specific adhesive properties, the polyurethane-vinyl polymerhybrid dispersions according to the invention can be mixed with otherdispersions or solutions of plastics (see above). Crosslinking agents,such as, for example, polyisocyanates or prepolymers having terminalisocyanate groups or water-soluble or -emulsifiable melamine orbenzoguanamine resins, can furthermore be added to improve theresistance to heat and peeling.

The adhesives based on the polyurethane-vinyl polymer hybrid dispersionsaccording to the invention can contain the additives customary inadhesives technology, such as plasticizers, solvents, film-bindingauxiliaries, fillers and synthetic and naturally occurring resins. Theyare specifically suitable for the production of gluings of substrates inthe motor vehicle industry, for example gluing of interior finishings,and in the shoe industry, for example for gluing the shoe sole and shoeshaft. The adhesives based on the polyurethane-vinyl polymer hybriddispersions according to the invention are prepared and processed by thecustomary methods of adhesives technology used for aqueous dispersionand solution adhesives.

The invention is further illustrated by the examples that follow.

EXAMPLES

In the specification and the examples, the following symbols are used:

-   M molar mass, SI unit: g/mol-   n amount of substance, SI unit: mol-   q dynamic viscosity, SI unit: Pa·s, determined in accordance with    DIN EN ISO 3219, at 23° C. and a shear rate of 100 s⁻¹ (if not    stated differently)-   w_(B) mass fraction of substance B in a mixture M, which mixture may    be a solution, SI unit: kg/kg, or any multiple thereof, such as    cg/g=10 g/kg=g/(100 g)=%, defined as-   w_(B)=m_(B)/m_(M)a, where m_(B) is the mass of substance B, and    m_(M) is the mass of the mixture or solution, this quantity also    referred to as “strength” when used for aqueously diluted acids or    bases-   w_(s) mass fraction of non-volatile matter, determined in accordance    with DIN EN ISO 3251 on a sample of 1 g, dried at 105° C. for one    hour-   w_(OH) hydroxyl value or hydroxyl number, ratio of the mass m_(K)OH    which has the same amount of substance of hydroxyl groups, —OH, as    the sample B, and the mass m_(n) of the sample B, determined in    accordance with DIN EN ISO 4629, the usual unit is “mg/g”-   w_(H) acid value or acid number, ratio of the mass m_(KOH) which is    needed to neutralise a sample B having acidic hydrogen groups H, and    the mass m_(B) of the sample B, determined in accordance with DIN EN    ISO 2114, the usual unit is “mg/g”-   w(H) mass fraction of polymer derived from monomers H1 and H2 in the    polyurethane-vinyl polymer hybrid resin, calculated as w(H)=m(H)    /[m(U)+m(H)], where m(U) is the mass of the polyurethane part-   pH the negative decadic logarithm of the numeric value of the molar    concentration of hydrogen ions, H⁺, in mol/L, defined as pH=−Ig    [c(H⁺)/(mol·L⁻¹)], determined in accordance with DIN ISO 976 on an    aqueously diluted sample having a mass fraction of solids of 10%-   T_(g) glass transition temperature, measured by dynamic scanning    calorimetry with a heating rate of 10 K/min (in these examples,    measured on polymers of monomers H1 and H2 in the ratio as used in    the example, the polymer having a degree of polymerisation which is    high enough so that T_(g) is not dependent on the degree of    polymerisation anymore)

Preparation of Polyester A′ (Comparative Example)

A mixture of 47 g of 1,6-hexanediol (M=118.18 g/mol; n=0.398 mol), 33.5g of adipic acid (M=146.14 g/mol; n=0.229 mol), and 22 g of isophthalicacid (M=166.13 g/mol; n=0.132 mol) was charged and heated to 220° C. Theamount of substance of functional groups in the reactant mixture was:n(OH)=0.795 mol; n(COOH)=0.458 mol+0.265 mol=0.723 mol. Water formed inthe reaction was distilled off with the aid 8 g of xylene added as anazeotrope former. After having reached the theoretical amount of water(14 g) and an acid value as determined on a sample of below 3 mg/g, theresidual xylene was distilled off, and the polyester was allowed to cooldown to room temperature (23° C.).

hydroxyl value: 45 mg/g; acid number: 2.8 mg/g

Preparation of Polyester A

89.4 g of polyester A′ were reacted with 1.4 g of the glycidyl ester ofneodecanoic acid (®Cardura E 10P, sold by Momentive Specialty ChemicalsInc.) at a temperature between 180° C. and 200° C. for about one houruntil the acid value as determined on a sample was below 0.1 mg/g.hydroxyl value: 45 mg/g; acid number 0.08 mg/g

Example 1 (Comparative Example)

863 g of polyester A′ were heated to 130° C. together with 79 g ofdimethylolpropionic acid (DMPA) and the mixture was kept at thistemperature until a homogeneous solution was formed. 150 g oftetramethylxylylene diisocyanate (TMXDI) were then metered in over aperiod of from thirty to forty-five minutes, while stirring wascontinued at 130° C. until no more free isocyanate groups could bedetected.

After cooling to 70° C., a solution consisting of 360 g of 2-ethylhexylacrylate, 36 g of glycerol monomethacrylate, 18 g of 1,4-butyleneglycoland 0.66 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added rapidlyand the mixture was homogenised. 244 g of TMXDI were added over a periodof fifteen minutes, and the components were reacted at 75° C. until themass fraction of free isocyanate groups in current reaction mixture was1.2%. Immediately after reaching this mass fraction of free isocyanategroups, 49 g of diethanolamine were added, and the reaction mixture washeld at the resulting temperature and stirred for sixty minutes. Afteraddition of 38 g of N,N-dimethylethanolamine, the mixture washomogenised for ten minutes. 3012 g of water having a temperature of 75°C. were then added to the prepolymer solution, while stirringintensively. After cooling the mixture to 75° C., the mixture wasstirred for a further hour. 2.4 g of an aqueous solution of tert-butylhydroperoxide having a mass fraction of solute of 70% was added, and theresulting mixture was homogenised for five minutes at 75° C. Then, amixture of 25 g water and 3.5 g ascorbic acid was added over a period ofbetween thirty and forty-five minutes. The temperature was then kept atbetween 75° C. and 80° C. for two further hours. After cooling to roomtemperature (23° C.), the resulting dispersion was filtered through afilter having a pore size of 25 μm. The dispersion thus obtained had thefollowing characteristic data:

w_(s)=36.4%; pH=7.9; η=69 mPa·s; T_(g)=−56° C.; w(H)=22%

Example 2 (Comparative Example)

950 g of polyester A′ were heated to 130° C. together with 111 g ofdimethylolpropionic acid (DMPA), and the mixture was kept at thistemperature under stirring until a homogeneous solution was obtained.206 g of tetramethylxylylene diisocyanate (TMXDI) were then metered inover a period of from thirty to forty-five minutes, while stirring wascontinued at 130° C. until no more free isocyanate groups were detected.After cooling to 70° C., a solution consisting of 246 g 2-ethylhexylacrylate, 610 g of methyl methacrylate, 88 g of glycerolmonomethacrylate, 2.47 g of 1,4-butyleneglycol and 2.3 g of2,6-di-tert-butyl-4-methylphenol (BHT) was added rapidly and the mixturewas homogenised. 301 g of TMXDI were then added over a period of fifteenminutes, and the components were then reacted at 75° C. until the massfraction of free isocyanate groups in the current reaction mixture was0.98%. Immediately after reaching this concentration of free isocyanategroups, a mixture which has a temperature of from 70° C. to 75° C.,composed of 25.8 g of 1,5-diamino-2-methylpentane, 56 g ofN,N-dimethylethanolamine and 4315 g of water were added and stirredintensively at 75° C. for sixty minutes. Then, 5.5 g of an aqueoussolution of tert-butyl hydroperoxide having a mass fraction of solute of70% was added, and the resulting mixture was homogenised for fiveminutes at from 70° C. to 75° C. After homogenisation, a mixture of 130g of water and 7.6 g of ascorbic acid was added over a period of fromthirty to forty-five minutes. Temperature was then kept at between 75°C. and 80° C. for two further hours. After cooling to room temperature(23° C.), the dispersion was filtered through a filter having a poresize of 25 μm. The dispersion thus obtained has following characteristicproperties: mass fraction of non-volatile matter w_(s)=36.1%; pH=7.7;η=230 mPa·s; T_(g)=42° C.; w(H)=37%

Example 3

950 g of polyester A were heated to 130° C. together with 98 g ofdimethylolpropionic acid (DMPA) and the mixture was kept at thistemperature until a homogeneous solution was obtained. 190 g oftetramethylxylylene diisocyanate (TMXDI) were then metered in over aperiod of from thirty to forty-five minutes, while stirring wascontinued at 130° C. until no free isocyanate groups could be detected.After cooling to 70° C., a solution consisting of 625 g of 2-ethylhexylacrylate, 368.6 g of methyl methacrylate, 88 g of glycerolmonomethacrylate and 2.3 g of 2,6-di-tert-butyl-4-methylphenol (BHT) wasadded rapidly and the resulting mixture was homogenised. A mixture of124 g TMXDI and 143 g of5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethyl-cyclohexane (IPDI)were then added over a period of fifteen minutes, and the mixture wassubjected to reaction at 75° C. until the mass fraction of freeisocyanate groups in the current reaction mixture was 0.88%. Immediatelyafter reaching this concentration of free isocyanate groups, a mixturehaving a temperature of from 70° C. to 75° C., composed of 23.8 g of2-methyl-1,5-pentanediamine, 58.6 g of N,N-dimethylethanolamine and 4335g of water were added and stirred intensively at 75° C. for sixtyminutes. Afterwards, 6.28 g of an aqueous solution oftert-butylhydroperoxide having a mass fraction of solute of 70% wasadded and the resulting mixture was homogenised for five minutes at from70° C. to 75° C. After homogenisation, a mixture of 190 g of water and8.7 g of ascorbic acid was added over a period of from thirty toforty-five minutes. Temperature was then kept at between 75° C. and 80°C. for two further hours. After cooling to room temperature (23° C.),the dispersion was filtered through a filter having a pore size of 25μm. The dispersion thus obtained has following characteristics:w_(s)=35.8%; pH=8.4; η=310 mPa·s; T_(g)=−10° C.; w(H)=41%

Example 4

950 g of polyester A were heated to 130° C. together with 98 g ofdimethylolpropionic acid (DMPA) and the mixture was kept at thistemperature until a homogeneous solution was obtained. 190 g oftetramethylxylylene diisocyanate (TMXDI) were then metered in over aperiod of from thirty to forty-five minutes, while stirring wascontinued at 130° C. until no free isocyanate groups were detected.

After cooling to 70° C., a solution consisting of 709 g of 2-ethylhexylacrylate, 419 g of methyl methacrylate, 24.8 g of 1,6-hexanedioldiacrylate, 88 g of glycerol monomethacrylate, 60 g of 1,4-butanedioland 2.3 g of 2,6-di-tert-butyl-4-methylphenol (BHT) was added rapidlyand the mixture was homogenised. 469 g of TMXDI are added over a periodof fifteen minutes and the components were reacted at 75° C. until themass fraction of free isocyanate groups in the reaction mixture was1.04%. Immediately after reaching this concentration of free isocyanategroups, a mixture having a temperature of from 70° C. to 75° C.,composed of 16.4 g of 2-methyl-1,5-pentanediamine, 29.3 g ofdiethanolamine, 58.5 g of N,N-dimethylethanolamine and 5097 g of waterwere added and stirred intensively at 75° C. for sixty minutes.Afterwards, 7.21 g of an aqueous solution of tert-butylhydroperoxidehaving a mass fraction of solute of 70% was added, and the resultantmixture was homogenised for five minutes at between 70° C. and 75° C.After homogenisation, a mixture of 230 g of water and 10 g of ascorbicacid was added over a period of thirty to forty-five minutes.Temperature was then kept at between 75° C. and 80° C. for two furtherhours. After cooling to room temperature (23° C.), the dispersion wasfiltered through a filter having a pore size of 25 μm. The dispersionthus obtained had the following characteristics: w_(s)=35.8% (1 h; 125°C.; 1 g); pH=8.4; η=310 mPa·s; T_(g)=−10° C.; w(H)=40%

Example 5

950 g of polyester A were heated to 130° C. together with 98 g ofdimethylolpropionic acid (DMPA) and the mixture was kept at thistemperature until a homogeneous solution was formed. 190 g oftetramethylxylylene diisoxyanate (TMXDI) were then metered in over aperiod of from thirty to forty-five minutes, while stirring wascontinued at 130° C. until no more free isocyanate groups could bedetected.

After cooling to 70° C., a solution consisting of 182 g of 2-ethylhexylacrylate, 757 g of methyl methacrylate, 21 g of 1,6-hexanedioldiacrylate, 88 g of glycerol monomethacrylate, and 2.3 g of2,6-di-tert-butyl-4-methylphenol (BHT) was added rapidly, and themixture was homogenised. A mixture of 124 g of TMXDI and 143 g of IPDIwere added over a period of fifteen minutes, and the components werereacted at 75° C. until the mass fraction of free isocyanate groups inthe current reaction mixture was 0.9%. Immediately after reaching thismass fraction of free isocyanate groups, a mixture which had atemperature of from 70° C. to 75° C., composed of 12 g of2-methyl-1,5-pentanediamine, 20.9 g of diethanolamine, 58.5 g ofdimethylethanolamine and 4320 g of water were added and stirredintensively at 75° C. for one hour. Afterwards, 6.1 g of an aqueoussolution of tert-butylhydroperoxide having a mass fraction of solute of70% was added and homogenised for five minutes at from 70° C. to 75° C.After homogenisation, a mixture of 190 g of water and 8.4 g od ascorbicacid was added over a period of from thirty to forty-five minutes.Temperature was then kept between 75° C. and 80° C. for two furtherhours. After cooling to room temperature (23° C.), the dispersion wasfiltered through a filter having a pore size of 25 μm. The dispersionthus obtained has following key figures: w_(s)=35.6%; pH=7.9; η=120mPa·s; T_(g)=60° C.; w(H)=40%

Example 6

950 g of polyester A were heated to 130° C. together with 98 g ofdimethylolpropionic acid (DMPA) and the mixture was kept at thistemperature until a homogeneous solution was formed. 190 g oftetramethylxylylene diisoxyanate (TMXDI) were then metered in over aperiod of from thirty to forty-five minutes, while stirring wascontinued at 130° C. until no more free isocyanate groups could bedetected.

After cooling to 70° C., a solution consisting of 61.1 g of 2-ethylhexylacrylate, 254 g of methyl methacrylate, 88 g of glycerolmonomethacrylate, and 2.3 g of 2,6-di-tert-butyl-4-methylphenol (BHT)was added rapidly and the mixture was homogenised. 280.5 g of TMXDI wereadded over a period of fifteen minutes, and the components were reactedat 75° C. until the mass fraction of free isocyanate groups in thecurrent reaction mixture was 1.2%. Immediately after reaching this massfraction of free isocyanate groups, a mixture which had a temperature ofbetween 70° C. and 75° C. was added, composed of 23.5 g of2-methyl-1,5-pentanediamine, 58.5 g of dimethylethanolamine, and 3288 gof water were added and stirred intensively at 75° C. for one hour.Afterwards, 2.34 g of an aqueous solution of tert-butylhydroperoxidehaving a mass fraction of solute of 70% was added and homogenised forfive minutes at between 70° C. and 75° C. After homogenisation, amixture of 100 g of water and 3.24 g of ascorbic acid was added over aperiod of from thirty to forty-five minutes. Temperature was then keptat between 75° C. and 80° C. for two further hours. After cooling toroom temperature (23° C.), the dispersion was filtered through a filterhaving a pore size of 25 μm. The dispersion thus obtained has followingkey figures: w_(s)=35.2%; pH=8.1; η=230 mPa·s; T_(g)=60° C.; w(H)=20%

Application test were conducted using steel sheets coated with a usualmulti-layer coating as used in car bodies by the automotive industry.The following paints were prepared therefor:

Example 7 CED Resin

2572 g of an epoxy resin based on bisphenol A, having a number averagemolar mass of 380 g/mol, 440 g of a polycaprolactone diol having anumber average molar mass of 550 g/mol, 661 g of bisphenol A, and 1734 gof methoxypropanol were sequentially filled into a resin kettle, andheated under stirring to 43° C. The mixture was stirred for furtherthirty minutes, and then cooled to 41° C. At this temperature, 221 g ofdiethanolamine and then, 194 g of dimethylaminopropylamine, were added,whereupon the temperature rose to a maximum of 125° C. under cooling.After continuing the reaction for two more hours under stirring at 125°C., the dynamic viscosity of a sample drawn and diluted to a massfraction of 40% with methoxypropanol, measured at 23° C. and a shearrate of 25 s⁻¹, was 765 mPa·s. The reaction mass was then cooled to 120°C.

Example 8 CED Curing Agent

In a separate step, 105 g of diethanolamine and 102 g of propylenecarbonate were reacted to form an adduct at 120° C. for three hours.

687.5 g of MDI were charged under exclusion of humidity into a resinkettle. At 25° C., 445.5 g of diethylene glycol monobutylether wereslowly added under gentle cooling, keeping the temperature at a maximumof 40° C. The mass fraction of isocyanate groups, calculated as —N═C═O,molar mass 42.02 g/mol, was 9.9%. At a temperature of 40° C., 207 g ofthe adduct made in the first step were added together with 0.4 g ofdibutyltin dilaurate. Due to the exothermic reaction, the temperaturerose to 80° C. which was kept as upper limit by cooling. Reaction wascontinued under stirring for three hours at that temperature. 5 g ofethanol and 61.8 g of methoxypropanol were then added at 80° C., andstirring was continued for one further hour. 60 g of water were thenadded, and the mixture was homogenised while lowering the temperature toambient (23° C.).

Example 9 CED Resin Emulsion

5822 g of the resin solution of Example 7 were charged to a reactionvessel, and heated to 120° C. under stirring. 1426 g of methoxypropanolwere distilled off at that temperature under reduced pressure. Then, theremaining liquid was cooled to 95° C., and 107 g of deionised water wereadded, thus lowering the temperature to 80° C. 2408 g of the curingagent of Example 8 were then added, and the mixture was homogenised at80° C. for one hour.

In a separate step, an acidic catalyst solution was prepared bydissolving 107 g of bismuth trioxide in 298.3 g of an aqueous solutionof methanesulfonic acid with a mass fraction of solute of 70%, anddiluting after complete dissolution by adding 7913 g of deionised water.The homogenised mixture of resin and curing agent was then added to thiscatalyst solution within thirty minutes under thorough stirring, wherebythe mixture assumed a temperature of 40° C. The mixture was stirred fortwo more hours at this temperature, and then diluted by addition of 2058g of deionised water to a mass fraction of solids of 37%.

Example 10 Grinding Resin

258 g of 2-ethylhexylamine were charged into a resin kettle equippedwith a stirrer, a thermometer and distillation facilities and heated to80° C. At this temperature, 380 g of an epoxy resin made frompolypropylene glycol and epichlorohydrin, having a specific content ofepoxide groups of 5.26 mol/kg, were added evenly over one hour with thetemperature rising to 120° C. The reaction was continued at 120° C. forone further hour. Next, 1175 g of 2-butoxyethanol were added, and thetemperature was lowered to 70° C. whereupon 1900 g of an epoxy resinbased on bisphenol A and epichlorohydrin having a specific content ofepoxide groups of 2.11 mol/kg were added. The mixture was heated to 120°C. and left to react for ninety minutes. The intermediate thus obtainedhas a mass fraction of polyoxyalkylene units (—CH(CH₃)—CH₂—O—) of 11%,and a mass fraction of alkyl groups having more than three carbon atoms,of 9%.

This intermediate was brought to a temperature of 100° C., and 204 g of3-(N,N-dimethyl)-aminopropylamine-1 were added, and the mixture wasreacted at 100° C. for one hour. 314 g of 2-butoxyethanol were thenadded, together with 66 g of paraformaldehyde having a mass fraction offormaldehyde of 91%. The temperature was raised to 140° C., and 36 g ofwater formed in the reaction were distilled off azeotropically usingmethyl isobutylketone as carrier. When the water was separated, theketone was removed by distillation under reduced pressure, and theremainder was diluted to a mass fraction of solids of 55% by adding 774g of 2-butoxyethanol.

Example 11 Pigment Paste

The following materials were added to a mixing vessel in the ordershown: 207.9 g of deionised water, 16.9 g of aqueous acetic acid (30 gof acetic acid in 100 g of the aqueously diluted solution), 18.7 g of2-butoxyethanol, 268 g of the grinding resin solution of Example 10,10.2 g of a 50% strength solution of2,4,7,9-tetramethyl-5-decyne-4,6-diol in 2-butoxyethanol (®Surfynol 104BC, Air Products Nederland B. V.), 7.3 g of a carbon black pigment(®Printex 201, Evonik Industries), and 479.2 g of a titanium dioxidewhite pigment (®Kronos RN 59, Kronos Titan GmbH). The mixture wasdispersed in a dissolver for fifteen minutes, and then ground in a ballmill for one hour.

Example 12 Preparation of CED Coating Composition

CED coating compositions were prepared from the emulsion of example 9,the pigment paste of example 11 and water, according to the followingrecipe:

3392 g CED Resin Emulsion (Example 9)

5982 g deionised water626 g pigment paste (Example 11)

The ingredients were blended in the order shown under stirring andhomogenised for thirty minutes at 23° C.

Example 13 Preparation of Primer/Surfacer Coating Composition

The primer-surfacer coating composition 13b used was prepared from agrey pigment paste 13ba that was completed by addition of a blend 13bbconsisting of the condensation product of example 13ac which had beenadjusted to a mass fraction of solids of 42% by addition of deionisedwater, the aqueous dispersion of example 13ad and a highlymethoxymethylated melamine crosslinker.

Example 13aa—Acid Functional Polyurethane

In a first reaction, an acid functional polyurethane 13aa was preparedby charging, in a resin kettle, a mixture of 810 g ofdimethylolpropionic acid in a mixture of 946 g of diethylene glycoldimethyl ether and 526 g of methyl isobutyl ketone and heating thismixture to 100° C. until complete dissolution. At this temperature, amixture of 870 g of toluylene diisocyanate (“TDI”) and 528 g of asemicapped TDI which is a reaction product of one mol of TDI with onemol of ethyleneglycol monoethylether was added over four hours whilekeeping the temperature constant at 100° C. The reaction mixture wasstirred at this temperature for one hour in order to completeconsumption of all isocyanate groups. The mass fraction of solids was60%. This acid functional polyurethane 13aa had an acid number of 140mg/g and a Staudinger-Index of 9.3 cm³/g, measured on solutions inN,N-dimethylformamide (DMF) at 20° C.

The semi-capped TDI was prepared separately by addition of 300 g ofethylene glycol mono-ethylether to 580 g of TDI within two hours at 30°C. and subsequent reaction for two more hours after which time a finalmass fraction of isocyanate groups in the adduct of 16.5% was found.

Example 13ab—Hydroxy-Functional Polyester

In a separate step, a hydroxy-functional polyester 13ab was prepared bymixing in a resin kettle, 190 g of tripropylene glycol, 625 g ofneopentyl glycol, 140 g of isomerised linoleic acid, 415 g ofisophthalic acid, and 290 g of trimellitic acid anhydride, andesterification at 230° C. until the acid number of the reaction mixturehad decreased to 4 mg/g. The efflux time of a 50% strength solution in2-n-butoxyethanol of the resin formed, measured according to DIN 53211at 20° C., was 165 s. The value of the Staudinger index of thehydroxyfunctional polyester 13ab, measured in N,N-dimethylformamide at20° C., was 10.5 cm³/g.

Example 13ac—Condensation Product 13ac of the Acid FunctionalPolyurethane of Example 13aa and the Hydroxy-Functional Polyester ofExample 13ab

300 g of the acid functional polyurethane of example 13aa and 700 g ofthe hydroxy-functional polyester of example 13ab were charged to areaction vessel equipped with stirrer, thermometer, nitrogen inlet, anddistillation apparatus, mixed and heated under stirring to 155° C. Thesolvents were removed under a nitrogen blanket by distillation underreduced pressure to maintain a steady flow of separated solvent in thecondenser. The progress of the reaction was monitored by drawing samplesand analysing for acid number and viscosity. The reaction was stoppedwhen an acid number of 36 mg/g and a Staudinger index of 16.2 cm³/g hadbeen reached, and the condensation product was then cooled to ambienttemperature (23° C.) and discharged. This condensation product referredto as 13ac was fully dilutable in water after neutralisation withdimethylethanolamine, with no sedimentation or phase separation.

Example 13ad—Modified Polyester

A resin kettle equipped with stirrer and reflux condenser was chargedwith 192 g of tri-propylene glycol and 104 g of neopentyl glycol, thecharge was heated under stirring to 110° C. 192 g of trimellithicanhydride were then added, and the mixture was heated within two hoursto 170° C. The reaction mixture was held at that temperature until theacid number was 87 mg/g. After cooling to 150° C., 40 g of a commercialmixture of glycidyl esters of alpha-branched decanoic acids (®Cardura E10, Momentive Specialty Chemicals, Inc.) and 14 g of linseed oil fattyacid were added. This mixture was then heated to 180° C. within onehour, and held at that temperature until an acid number of 55 mg/g wasreached. The reaction mixture was then cooled and diluted by addition ofmethoxypropanol to a mass fraction of solids of 70%. To 100 g of thissolution, 7 g of dimethyl ethanolamine, and 68 g of deionised water wereadded and homogenised with a mechanical stirrer for fifteen minutes at600 min⁻¹. An aqueous dispersion with a mass fraction of solids of 40%was obtained.

Example 13b—Preparation of the Pigmented Primer-Surfacer CoatingComposition

A pigmented primer-surfacer coating composition was prepared accordingto the following recipe: To 21.10 g of the condensation product ofexample 13ac which had been adjusted to a mass fraction of solids of 42%by addition of deionised water was charged, in the sequence stated, 3.35g of deionised water, 12.65 g of a rutil-type titanium dioxide pigment(surface treated with A1 and Zr compounds, ®Kronos 2190, Kronos TitanGmbH), 12.65 g of precipitated barium sulfate pigment (Blanc fixe F,Sachtleben GmbH), and 0.05 g of carbon black (®Printex U, Evonik CarbonBlack GmbH), and then homogenised with a mechanical stirrer at 1200min⁻¹ for fifteen minutes. This pre-blend was transferred to a bead milland ground at a temperature not exceeding 50° C. After a milling time offorty-five minutes, the required particle size of 10 μm was achieved,grinding was stopped and the paste referred to as 13ba thus formed wasseparated from the beads.

A mixture 13bb was prepared by charging 9.00 g of the condensationproduct of example 13ac which had been adjusted to a mass fraction ofsolids of 42% by addition of deionised water, and adding in thissequence, 27.20 g of the aqueous dispersion of example 13ad, 1.75 g of ahighly methoxymethylated melamine crosslinker having a molar ratio ofmethoxy groups to methylene groups to melamine derived moieties of from5.0 mol:5.8 mol:1 mol (Cymel® 303, Allnex USA Inc.), and 12 g ofdeionised water.

This mixture 13bb was added to the paste 13ba at ambient temperature(23° C.) and homogenised with a mechanical stirrer at 1200 min⁻¹ forfifteen minutes to obtain the pigmented primer-surfacer coatingcomposition 13b. Dynamic viscosity of this coating composition 13b was300 mPa·s (measured at a shear rate of 25 s⁻¹), and its pH value was8.0.

Example 14 Preparation of Basecoat Coating Compositions

Basecoat coating compositions were prepared from the polyurethane-vinylpolymer hybrid dispersions of examples 1 to 6, according to thefollowing recipe in Table 1:

TABLE 1 Basecoat compositions (mass of constituents in g) polyurethane -vinyl polymer hybrid dispersion (w_(s) = 351.2 Part A 36%) Cymel ® 32715.6 Part A DMEA 10% in water 14.4 Part A H₂O deionised 115.2 Part ARheovis ® AS 1130 (10% strength in water) 87.4 Part B H₂O deionised227.9 Part B Aluminum flakes (Hydrolan ® 2154) 93.6 Part C Additol ® XL250 6 Part C Butylglycol 69.2 Part C Isobutanol 19.5 Part D

A basecoat composition was prepared according to the following recipe:the polyurethane-vinyl polymer hybrid dispersion (Example 1 to Example6) was charged, in the sequence stated a methylated high imino melaminecrosslinker (Cymel® 327, Allnex USA Inc.), dimethyl ethanolamine (a 10%strength solution in deionised water) and deionised water (Part A) wereadded to this charge and then homogenised with a mechanical stirrer at900 min⁻¹. After fifteen minutes stirring, a 10% strength solution of anacrylic copolymer thickener in deionised water (Rheovis® AS 1130, BASFSE) and further deionised water (Part B) were added and homogenised foranother ten minutes at 900 min⁻¹. The aluminum flake slurry (Part C) wasprepared in a separate step by charging the aluminum flakes (silicaencapsulated aluminium flakes, Hydrolan®2154, Eckart GmbH), adding theanionic wetting agent (Additol XL® 250, Allnex Austria GmbH) andbutylglycol (ethylene glycol monobutyl ether) and homogenising with amechanical stirrer at 600 min⁻¹ for thirty minutes. The homogenised PartC was then added with stirring at 900 min⁻¹ to the preblended Part A andB, and homogenised for another twenty minutes. In the last step,isobutanol (Part D) was added and the mixture was homogenised foranother five minutes at 900 min⁻¹.

The basecoat coating compositions prepared as described were allowed torest for twelve hours at ambient temperature (23° C.). After this timethe pH value was adjusted to 8.3 by means of a 10% strength solution ofdimethylethanolamine in deionised water, and the viscosity of the paintswas adjusted to 300 mPa·s (measured at a shear rate of 25 s⁻¹), byadding deionised water. Their composition is detailed in Table 2.

TABLE 2 Basecoat Paint Compositions (masses of constituents in g)constituent L1 L2 L3 L4 L5 L6 dispersion of Example 1 347.3 — — — — —(comp) dispersion of Example 2 — 350.2 — — — — (comp) dispersion ofExample 3 — — 353.2 — — — dispersion of Example 4 — — — 353.2 — —dispersion of Example 5 — — — — 355.1 — dispersion of Example 6 — — — —— 359.2 Cymel ® 327 15.6 15.6 15.6 15.6 15.6 15.6 DMEA 10% in water 14.414.4 14.4 14.4 14.4 14.4 H₂O deionised 115.2 115.2 115.2 115.2 115.2115.2 Rheovis ® AS 1130 87.4 87.4 87.4 87.4 87.4 87.4 (10% strength inwater) H₂O deionised 227.9 227.9 227.9 227.9 227.9 227.9 aluminum flakes(Hydrolan ® 93.6 93.6 93.6 93.6 93.6 93.6 2154) Additol ® XL 250 6 6 6 66 6 butylglycol 69.2 69.2 69.2 69.2 69.2 69.2 isobutanol 19.5 19.5 19.519.5 19.5 19.5

Example 15 Preparation of Clearcoat Coating Composition Example15a—Hydroxy-Functional Acrylic Polymer

An Acrylic Copolymer was Made According to the Following Recipe:

Into a recator equipped with a stirrer, in inert gas inlet, a heatingand cooling system, and an addition funnel, the glycidylester ofneodecanoic acid was charged and heated to 175° C. Within six hours, amonomer and initiator mixture was continuously added that consisted of74.8 g of acrylic acid, 229.3 g of hydroxyethylmethacrylate, 178.3 g oftert-butylmethacrylate, 62.7 g of methylmethacrylate, and 222.4 g ofstyrene, together with 19.8 g of di-tert-amyl peroxide, and a polymerwas formed. The reaction mixture was stirred for two further hours, bywhen more than 95% of conversion was noted. The copolymer was diluted byaddition of butyl acetate to a mass fraction of solids of 75%, thesolution was filtered after cooling to room temperature to removesuspended solids, and the mass fraction of solids was then adjusted to70% by addition of further butyl acetate.

Example 15b—Preparation of the Clearcoat Coating Composition

Two pre-mixtures were prepared according to the following recipes:

Part A:

825 g of the hydroxy-functional acrylic polymer solution of Example 15a51 g of butylacetate51 g of xylene51 g of methoxypropyl acetate5 g of a hindered amine light stabiliser (mixture ofbis-(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate and1-(methyl)-8-(1,2,2,6,6,pentamethyl-4-piperidinyl)sebacate, sold asTinuvin® 292 by BASF SE) 15 g of a benzotriazole type light stabiliser(mixture ofβ-[3-(2-H-benzotriazole-2-yl)-4-hydroxy-5-tert.butylphenyl]-propionicacid poly[ethylene glycol] 300-ester andbis{β-[3-(2-H-benzo-triazole-2-yl)-4-hydroxy-5-tert.butylphenyl]-propionicacid}-poly(ethylene glycol) 300-ester sold as Tinuvin® 1130, BASF SE)2 g of a levelling agent based on a modified silicone (Additol® VXL4930, Allnex Austria GmbH)

Part B:

322 g of HDI trimer dissolved in butylacetate, mass fraction of solute90% (Desmodur® N 3390 BA, Isocyanurate type, CAS Nr.: 28182-81-2, soldby Bayer Material Science AG)97 g of butylacetate40 g of xylene24 g of Solvent naphtha 150/180 (blend of aromatic hydrocarbons with aboiling range of from 150° C. to 180° C.)

Components of Part A were charged in the order mentioned and homogenisedwith a mechanical stirrer for 15 minutes at 23° C. at 900 min⁻¹.

In a separate step, the solution of trimeric HDI, and solvents wereblended and added with stirring at 900 min⁻¹ to the preblended Part A.After ten minutes' homogenisation, the viscosity of the clearcoat wasadjusted to 130 mPa·s (measured at a shear rate of 25 s⁻¹), by adding amixture in a mass ratio of 60/40 of butyl acetate and solvent naphtha150/180. This ready to use clearcoat coating composition must be appliedwithin ninety minutes.

Example 16 Preparation of Multilayer Coatings

A multilayer coating was prepared from the CED coating composition ofexample 12, the primer-surfacer coating composition of example 13b, thebasecoat compositions of example 14 (paints L1 to L6), and the clearcoatcoating composition of example 15 according to the following procedure:

Preparation of the Test Panels:

12 Zinc-phosphated steel panels (®Gardobond 26S 6800° C. from Chemetall)were coated with the CED paint according to example 12 under followingconditions:temperature of CED-bath: 30° C.deposition time: 2 minvoltage: 300 V

All coated panels were allowed to flash off at ambient temperature forthirty minutes and were then stoved for twenty minutes at 180° C. Dryfilm thickness of the CED layer was 22 in for all panels. In the nextstep, the primer surfacer coating composition of example 13b was appliedto all 12 panels (dry film thickness 30 μm), and after a flash off step(ten minutes at 23° C.) stoved for twenty minutes at 165° C. In a thirdstep, the 12 panels were overcoated with the basecoat compositions ofexample 14 (paints L through L6, with 2 panels each for all paints Lthrough L6). The basecoat layers (10 μm dry film thickness) were allowedto flash off for ten minutes at 23° C. and were then stoved for tenminutes at 80° C. Finally all panels were overcoated with the clearcoatcomposition of example 15 (50 μm dry film thickness) and stoved fortwenty minutes at 140° C.

TABLE 3 detailed overview of the panel preparation Primer Panel CEDStoving Surfacer Stoving Basecoat Stoving Clearcoat Stoving P1 Ex. 12 20min; Ex. 13b 20 min; L1 10 min; Ex. 15b 20 min; 180° C. 165° C. 80° C.140° C. P1a Ex. 12 20 min; Ex. 13b 20 min; L1 10 min; Ex. 15b 20 min;180° C. 165° C. 80° C. 140° C. P2 Ex. 12 20 min; Ex. 13b 20 min; L2 10min; Ex. 15b 20 min; 180° C. 165° C. 80° C. 140° C. P2a Ex. 12 20 min;Ex. 13b 20 min; L2 10 min; Ex. 15b 20 min; 180° C. 165° C. 80° C. 140°C. P3 Ex. 12 20 min; Ex. 13b 20 min; L3 10 min; Ex. 15b 20 min; 180° C.165° C. 80° C. 140° C. P3a Ex. 12 20 min; Ex. 13b 20 min; L3 10 min; Ex.15b 20 min; 180° C. 165° C. 80° C. 140° C. P4 Ex. 12 20 min; Ex. 13b 20min; L4 10 min; Ex. 15b 20 min; 180° C. 165° C. 80° C. 140° C. P4a Ex.12 20 min; Ex. 13b 20 min; L4 10 min; Ex. 15b 20 min; 180° C. 165° C.80° C. 140° C. P5 Ex. 12 20 min; Ex. 13b 20 min; L5 10 min; Ex. 15b 20min; 180° C. 165° C. 80° C. 140° C. P5a Ex. 12 20 min; Ex. 13b 20 min;L5 10 min; Ex. 15b 20 min; 180° C. 165° C. 80° C. 140° C. P6 Ex. 12 20min; Ex. 13b 20 min; L6 10 min; Ex. 15b 20 min; 180° C. 165° C. 80° C.140° C. P6a Ex. 12 20 min; Ex. 13b 20 min; L6 10 min; Ex. 15b 20 min;180° C. 165° C. 80° C. 140° C.

Panels 1 to 6 (P1, P2, . . . P6) were exposed to a stone chip testaccording to DIN EN ISO 20567-1 (2×500 g of chips, transported with anair pressure of 0.2 MPa=2 bar), and panels 1a to 6a (P1a, P2a, . . .P6a) were used to run a humidity resistance testing according to DIN ENISO 6270-2 (condensation atmosphere with constant humidity, testduration 240 hours). After the test time, the panels were allowed toregenerate for one hour at 23° C. and a relative humidity of 65% beforethe panels were evaluated according to DIN EN ISO 4628-2 (Designation ofquantity and size of defects, and of intensity of uniform changes inappearance—Part 2: Assessment of degree of blistering).

The results obtained are shown in table 4.

TABLE 4 Test Results Panel Stone chip test rating Degree of blisteringP1 2-3 P1a 3 (S3) P2 3-4 P2a 4 (S3) P3 1 P3a No blisters P4 1-2 P4a Noblisters P5 2 P5a 2 (S2) P6 1-2 P6a 2 (S2)

This comparison shows that both stone chip test (indicating interlayeradhesion) and humidity resistance are markedly improved by use of ahydrophobically modified polyester as a basis for the polyurethane-vinylpolymer hybrid dispersion used in preparation of the base coat layer.This could not have been expected by a person skilled in the art.

1. Aqueous polyurethane-vinyl polymer hybrid dispersions comprising, asbuilding blocks, hydrophobically modified hydroxy-functional polyestersA, acids B that have further groups which react with isocyanates underformation of urethanes, ureas, or thiourethanes, optionally,hydroxy-functional oligomeric or polymeric compounds C which may bepolyesters, polycarbonates, polyethers, polyamides, polydienes andpolyenes, and which have at least two hydroxyl groups per molecule,optionally, monomeric hydroxy compounds D having at least two hydroxylgroups per molecule, optionally, compounds E having at least one primaryor secondary amino group, and at least one hydroxyl group per molecule,optionally, compounds F having two or more primary or secondary aminogroups per molecule and no hydroxyl groups, compounds G having only onehydroxyl group, and one or more tertiary amino groups, olefinicallyunsaturated monomers H2 having a polymerisable ethylenic unsaturationand a further functional group which reacts with an isocyanate groupunder bond formation, olefinically unsaturated monomers H1 having atleast one polymerisable ethylenic unsaturation and no further functionalgroup which reacts with an isocyanate group, and multifunctionalisocyanates I having at least two isocyanate groups per molecule,wherein the hydrophobically modified polyesters A are obtained from apolyester A′ having residual hydroxyl and acid groups, by reaction ofthe acid groups thereof with a mono-functional compound A4 having anepoxide or aziridine functionality, and a linear or branched alkylresidue of at least four carbon atoms, in which reaction at least 90% ofthe remaining acid groups of the polyester A′ are converted to ester oramide groups.
 2. The aqueous polyurethane-vinyl polymer hybriddispersions of claim 1 wherein the hydrophobically modified polyesters Ahave side chains with chain length of from four to twenty carbon atoms.3. The aqueous polyurethane-vinyl polymer hybrid dispersions of claim 1wherein the hydrophobically modified polyesters A have an acid number of0.1 mg/g or less.
 4. The aqueous polyurethane-vinyl polymer hybriddispersions of claim 2 wherein the side chains of the hydrophobicallymodified polyesters A are bound to the polyester by ester or amidegroups. 5-11. (canceled)
 12. A method of use of the aqueouspolyurethane-vinyl polymer hybrid dispersions of claim 1, for thepreparation of a coating composition, comprising the steps of providingthe aqueous polyurethane-vinyl polymer hybrid dispersions of claim 1,and adding thereto an aminoplast crosslinker, and homogenising theresulting mixture.
 13. A method of use of the aqueous polyurethane-vinylpolymer hybrid dispersions of claim 1, for the preparation of a coatingcomposition, comprising the steps of providing the aqueouspolyurethane-vinyl polymer hybrid dispersions of claim 1 and addingthereto an aminoplast crosslinker, homogenising the resulting mixture,applying the coating composition to a substrate, and crosslinking thecoating composition to form a coating, by heating the coated substrateto a temperature of from 50° C. to 180° C.